Methods for manufacturing a phase-change memory device

ABSTRACT

A method of manufacturing a phase-change memory device comprises forming a contact region on a substrate, forming a lower electrode electrically connected to the contact region, forming a phase-change material layer on the lower electrode using a chalcogenide compound target including carbon and metal, or carbon, nitrogen and metal, and forming an upper electrode on the phase-change material layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.11/860,931, filed Sep. 25, 2007, which is currently pending and claimspriority under 35 USC §119 to Korean Patent Application No.10-2006-94217 filed on Sep. 27, 2006, the contents of which areincorporated herein by reference in their entireties.

FIELD OF THE INVENTION

Example embodiments of the present invention relate to a chalcogenidecompound target, a method of forming the chalcogenide compound target,and a method of manufacturing a phase-change memory device. Moreparticularly, example embodiments of the present invention relate to achalcogenide compound target including a chalcogenide compound havingproper contents of ingredient, and a method of forming the chalcogenidecompound target, and a method of manufacturing a phase-change memorydevice including a phase-change material layer obtained using thechalcogenide compound target.

BACKGROUND OF THE INVENTION

Semiconductor memory devices are generally divided into volatilesemiconductor memory devices such as dynamic random access memory (DRAM)devices or static random access memory (SRAM) devices, and non-volatilesemiconductor memory devices such as flash memory devices orelectrically erasable programmable read only memory (EEPROM) devices.The volatile semiconductor memory device loses data stored therein whenpower is off. However, the non-volatile semiconductor memory devicekeeps stored data even if power is out.

Among the non-volatile semiconductor memory devices, the flash memorydevice has been widely employed in various electronic apparatuses suchas a digital camera, a cellular phone, an MP3 player, etc. Since aprogramming process and a reading process of the flash memory devicetake a relatively long time, technologies to manufacture a novelsemiconductor memory device, for example, a magnetic random accessmemory (MRAM) device, a ferroelectric random access memory (FRAM) deviceor a phase-change random access memory (PRAM) device, have beenconstantly developed.

The phase-change memory device stores information using a resistancedifference between an amorphous phase and a crystalline phase of aphase-change material layer composed of a chalcogenide compound, e.g.,germanium-antimony-tellurium (GST). Particularly, the PRAM device maystore data as states of “0” and “1” using a reversible phase transitionof the phase-change material layer. The amorphous phase of thephase-change material layer has a large resistance, whereas thecrystalline phase of the phase-change material layer has a relativelysmall resistance. In the PRAM device, a transistor formed on a substratemay provide the phase-change material layer with a reset current(I_(reset)) for changing the phase of the phase-change material layerfrom the crystalline state into the amorphous state. The transistor mayalso supply the phase-change material layer with a set current (I_(set))for changing the phase of the phase-change material layer from theamorphous state into the crystalline state. The conventional PRAM deviceis disclosed in U.S. Pat. No. 6,987,467, Korean Patent No. 546,406 andKorean Laid-Open Patent Publication No. 2006-1105.

In the conventional PRAM device, however, the phase-change materiallayer may not have proper properties so that the PRAM device may nothave desired electrical characteristics. For example, the phase-changematerial layer may be rapidly deteriorated, to thereby considerablyreduce data retention characteristics of the PRAM device. Additionally,the PRAM device may have a relatively great ser resistance when thephase-change material layer includes a normal GST compound.

Considering the above-mentioned problems, a phase-change material layerhas been formed using a chalcogenide compound doped into additionalelements such as nitrogen in order to improve electrical characteristicsof a PRAM device including the phase-change material layer. For example,Korean Laid-Open Patent Publication 2004-76225 discloses a phase-changememory device including a phase-change material layer composed of a GSTcompound doped with nitrogen. However, in the above-mentionedphase-change memory device having the phase-change material layerpattern of the GST compound doped with nitrogen, the phase-change memorydevice may have a considerably large initial writing current although aset resistance of the phase-change memory device may be decreased. Toimprove an integration degree of the phase-change memory device, adriving current of the phase-change memory device needs to be reduced.However, the set resistance of the phase-change memory device may begreatly increased in accordance with a reduction of the driving currentthereof when the phase-change material layer pattern of the phase-changememory device includes the GST compound doped with nitrogen only.Further, the phase-change memory device of GST compound doped withnitrogen may not ensure good adhesion strength relative to the firstelectrode and the second electrode. Thus, the first electrode and/or thesecond electrode may be separated from the phase-change material layerpattern, and also an interface resistance between the first electrodeand the phase-change material layer pattern or the second electrode andthe phase-change material layer pattern may be undesirably reduced.

Meanwhile, Korean Laid-Open Patent Publication No. 2005-4137 discloses asputtering target for forming a phase-change memory layer including aGST compound that contains nitrogen. However, the sputtering targetincludes carbon with a low content so that the phase-change memory layermay not have sufficient carbon content when the phase-change memorylayer is formed using the sputtering target. As a result, thephase-change memory layer may not have desired thermal and electricalcharacteristics when the phase-change memory layer is employed in aphase-change memory device.

SUMMARY OF THE INVENTION

Example embodiments of the present invention provide a chalcogenidecompound target including a chalcogenide compound that contains carbonand metal, or carbon, metal and nitrogen considering contents of carbon,metal and nitrogen.

Example embodiments of the present invention provide a method of forminga chalcogenide compound target including a chalcogenide compound thatcontains carbon and metal, or carbon, metal and nitrogen consideringcontents of carbon, metal and nitrogen.

Example embodiments of the present invention provide a method ofmanufacturing a phase-change memory device having a phase-changematerial layer formed using the chalcogenide compound target to ensureimproved electrical characteristics and reliability

According to one aspect of the present invention, there is provided achalcogenide compound target including a chalcogenide compound thatcontains carbon with a relatively high content and metal with arelatively low content.

In some example embodiments, the chalcogenide compound may have acomposition in accordance with the following chemical formula (1):

C_(A)M_(B)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (1)

In the above chemical formula (1), C indicates carbon, M representsmetal, 8.0≦A≦40.0, 0.1≦B≦20.0, 0.1≦X≦30.0 and 0.1≦Y≦90.0. Examples ofmetal may include aluminum (Al), gallium (Ga), chrome (Cr), manganese(Mn), iron (Fe), cobalt (Co), nickel (Ni), zirconium (Zr), molybdenum(Mo), ruthenium (Ru), palladium (Pd), hafnium (Hf), tantalum (Ta),iridium (Ir), platinum (Pt). These may be used alone or in a mixturethereof.

In some example embodiments, the chalcogenide compound target mayinclude a chalcogenide compound according to the following chemicalformula (2) in which germanium in the chemical formula (1) issubstituted with germanium and silicon (Si) or germanium and tin (Sn):

C_(A)M_(B)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (2)

In the above chemical formula (2), Z includes silicon or tin,0.1≦X≦80.0, and 0.1≦Y≦90.0.

In some example embodiments, the chalcogenide compound target mayinclude a chalcogenide compound according to the following chemicalformula (3) in which antimony in the chemical formula (1) is substitutedwith antimony and arsenic (As) or antimony and bismuth (Bi):

C_(A)M_(B)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B))   (3)

In the above chemical formula (3), T includes arsenic or bismuth,0.1≦X≦90.0, and 0.1≦Y≦80.0.

In some example embodiments, the chalcogenide compound target mayinclude a chalcogenide compound according to the following chemicalformula (4) in which tellurium in the chemical formula (1) issubstituted with antimony and selenium (Se):

C_(A)M_(B)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   (4)

In the above chemical formula (4), Q includes antimony and selenium,0.1≦X≦30.0, 0.1≦Y≦90.0, Q includes antimony and selenium, and0.1≦D≦80.0.

According to another aspect of the present invention, there is provideda chalcogenide compound target including a chalcogenide compound thatcontains carbon with a relatively high content, metal with a relativelylow content, and nitrogen with a relatively low content.

In some example embodiments, the chalcogenide compound may have acomposition in accordance with the following chemical formula (5):

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))   (5)

In the above chemical formula (5), C means carbon, M denotes metal, Nindicates nitrogen 8.0≦A≦40.0, 0.1≦B≦15.0, 0.1≦C≦10.0, 0.1≦X≦30.0 and0.1≦Y≦90.0.

In some example embodiments, the chalcogenide compound target mayinclude a chalcogenide compound according to the following chemicalformula (6) in which germanium in the chemical formula (5) issubstituted with germanium and silicon or germanium and tin:

C_(A)M_(B)N_(C)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))  (6)

In the above chemical formula (6), Z includes silicon or tin, 0.1≦X≦80.0and 0.1≦Y≦90.0.

In some example embodiments, the chalcogenide compound target mayinclude a chalcogenide compound according to the following chemicalformula (7) in which antimony in the chemical formula (5) is substitutedwith antimony and arsenic or antimony and bismuth:

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B-C))  (7)

In the above chemical formula (7), T includes arsenic or bismuth,0.1≦X≦90.0 and 0.1≦Y≦80.0.

In some example embodiments, the chalcogenide compound target mayinclude a chalcogenide compound according to the following chemicalformula (8) in which tellurium in the chemical formula (5) issubstituted with antimony and selenium:

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   (8)

In the above chemical formula (8), Q includes antimony and selenium,0.1≦X≦30.0, 0.1≦Y≦90.0, Q includes antimony and selenium, and0.1≦D≦80.0.

According to still another aspect of the present invention, there isprovided a method of forming a chalcogenide compound target. In themethod of forming the chalcogenide compound target, a first powderincluding germanium carbide or germanium is formed. A second powderincluding antimony carbide or antimony is prepared. A third powderincluding tellurium carbide or tellurium is formed. After a powdermixture by mixing the first to the third powders, the powder mixture isdried. A shaped body is formed by molding the powder mixture, and thenthe shaped body is sintered to obtain the a chalcogenide compoundtarget.

In some example embodiments, the germanium carbide may have acomposition in accordance with the following chemical formula (9):

C_(A)Ge_((100-A))   (9)

In the above chemical formula (9), C indicates carbon and 8.0≦A≦50.0.

In some example embodiments, the germanium carbide may have acomposition according to the following chemical formula (10) in whichgermanium in the chemical formula (9) is substituted with germanium andsilicon (Si) or germanium and tin (Sn):

C_(A)[Ge_(X)Z_((100-X))]_((100-A))   (10)

In the above chemical formula (10), Z includes silicon or tin and0.1≦X≦80.0.

In some example embodiments, the antimony carbide may have a compositionin accordance with the following chemical formula (11):

C_(A)Sb_((100-A))   (11)

In the above chemical formula (11), C indicates carbon and 8.0≦A≦50.0.

In some example embodiments, the antimony carbide may have a compositionaccording to the following chemical formula (12) in which antimony inthe chemical formula (11) is substituted with antimony and arsenic (As)or antimony and bismuth (Bi):

C_(A)[Sb_(Y)T_((100-Y))]_((100-A))   (12)

In the above chemical formula (12), T includes arsenic or bismuth and0.1≦Y≦80.0.

In some example embodiments, the tellurium carbide may have acomposition in accordance with the following chemical formula (13):

C_(A)Te_((100-A))   (13)

In the above chemical formula (13), C indicates carbon and 4.0≦A≦20.0.

In some example embodiments, the tellurium carbide may have acomposition according to the following chemical formula (14) in whichtellurium in the chemical formula (13) is substituted with antimony andselenium (Se):

C_(A)Q_((100-A))   (14)

In the above chemical formula (14), Q indicates antimony and selenium.

In some example embodiments, a fourth powder including metal carbide maybe additionally formed. The metal carbide may have a composition inaccordance with the following chemical formula (15):

C_(A)M_((100-A))   (15)

In the above chemical formula (15), M indicates metal. Examples of themetal carbide may include aluminum carbide, gallium carbide, indiumcarbide, titanium carbide, chrome carbide, manganese carbide, ironcarbide, nickel carbide, cobalt carbide, zirconium carbide, molybdenumcarbide, ruthenium carbide, palladium carbide, hafnium carbide, tantalumcarbide, iridium carbide, platinum carbide, etc. These may be used aloneor in a mixture thereof.

According to still another aspect of the present invention, there isprovided a method of manufacturing a phase-change memory device. In themethod of manufacturing the phase-change memory device, a contact regionis formed on a substrate. A lower electrode is formed on the substrate.The lower electrode is electrically connected to the contact region. Aphase-change material layer is formed on the lower electrode using achalcogenide compound target including carbon and metal, or carbon,nitrogen and metal. An upper electrode is formed on the phase-changematerial layer.

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (16):

C_(A)M_(B)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (16)

In the above chemical formula (16), C indicates carbon, M representsmetal, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦30.0 and 0.1≦Y≦90.0, and

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (17):

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))   (17)

In the above chemical formula (17), C means carbon, M denotes metal, Nindicates nitrogen 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦C≦10.0, 0.1≦X≦30.0 and0.1≦Y≦90.0.

According to still another aspect of the present invention, there isprovided a method of manufacturing a phase-change memory device. In themethod of manufacturing the phase-change memory device, a contact regionis formed on a substrate, and then a lower electrode is formed on thesubstrate. The lower electrode is electrically connected to the contactregion. A phase-change material layer is formed on the lower electrodeby a sputtering process using a first target including carbon or metalcarbide, and a second target including a chalcogenide compound. An upperelectrode is formed on the phase-change material layer.

In some example embodiments, a first power may be applied to the firsttarget, and a second power substantially different from the first powermay be applied to the second target. For example, the first power may bein a range of about 100 W to about 2,000 W, and the second power may bein a range of about 20 W to about 500 W.

In some example embodiments, the metal carbide may have a composition inaccordance with the following chemical formula (18):

C_(A)M_((100-A))   (18)

In the above chemical formula (18), M indicates metal, and 50.0≦A≦100.0.

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (19):

C_(A)M_(B)[Ge_(x)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (19)

In the above chemical formula (19), Z includes silicon or tin. Further,0.2≦A≦30.0, 0.1≦B≦15.0, 0.1X≦80.0 and 0.1≦Y≦90.0.

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (20):

C_(A)M_(B)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B))   (20)

In the above chemical formula (20), T includes arsenic or bismuth.Additionally, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦90.0, and 0.1≦Y≦80.0.

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (21):

C_(A)M_(B)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   21)

In the above chemical formula (21), Q includes antimony and selenium.Further, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦90.0 and 0.1≦Y≦90.0.

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (22):

C_(A)M_(B)N_(C)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))  (22)

In the above chemical formula (22), Z includes silicon or tin,0.1≦X≦80.0 and 0.1≦Y≦90.0. Additionally, 0.2≦A≦30.0, 0.1≦B≦15.0 and0.1≦C≦10.0.

In some example embodiments, the phase-change material layer may includea chalcogenide compound in accordance with the following chemicalformula (23):

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B-C))  (23)

In the above chemical formula (22), T includes arsenic or bismuth,0.1≦X≦90.0 and 0.1≦Y≦80.0. Further, 0.2≦A≦30.0, 0.1≦B≦15.0 and0.1≦C≦10.0.

According to the present invention, a chalcogenide compound target mayinclude a chalcogenide compound that contains carbon and metal, orcarbon, metal and nitrogen considering contents of carbon, metal andnitrogen. When a phase- change material layer is formed using thechalcogenide compound target by various sputtering processes, the phasetransition of the phase-change material layer may be stably repeated andalso the phase-change material layer may have enhanced crystallizedtemperature and resistance. Further, a phase-change memory device mayhave reduced set resistance and driving current while improvingdurability and sensing margin when the phase-change material layer isemployed in the phase- change memory device.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features and advantages of the present inventionwill become readily apparent by reference to the following detaileddescription when considered in conjunction with the accompanyingdrawings wherein:

FIG. 1 is a flow chart illustrating a method of forming a chalcogenidecompound target in accordance with example embodiments of the presentinvention;

FIGS. 2A to 2E are cross-sectional views illustrating a method ofmanufacturing a phase-change memory device in accordance with exampleembodiments of the present invention;

FIGS. 3A to 3D are cross-sectional views illustrating a method ofmanufacturing a phase-change memory device in accordance with exampleembodiments of the present invention; and

FIGS. 4A to 4C are cross-sectional views illustrating a method ofmanufacturing a phase-change memory device in accordance with exampleembodiments of the present invention.

DESCRIPTION OF THE EMBODIMENTS

The present invention is described more fully hereinafter with referenceto the accompanying drawings, in which example embodiments of thepresent invention are shown. The present invention may, however, beembodied in many different forms and should not be construed as limitedto the example embodiments set forth herein. Rather, these exampleembodiments are provided so that this disclosure will be thorough andcomplete, and will fully convey the scope of the present invention tothose skilled in the art. In the drawings, the sizes and relative sizesof layers and regions may be exaggerated for clarity.

It will be understood that when an element or layer is referred to asbeing “on,” “connected to” or “coupled to” another element or layer, itcan be directly on, connected or coupled to the other clement or layeror intervening elements or layers may be present. In contrast, when anelement is referred to as being “directly on,” “directly connected to”or “directly coupled to” another element or layer, there are nointervening elements or layers present. Like numbers refer to likeelements throughout. As used herein, the term “and/or” includes any andall combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, third etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms arconly used to distinguish one clement, component, region, layer orsection from another region, layer or section. Thus, a first element,component, region, layer or section discussed below could be termed asecond element, component, region, layer or section without departingfrom the teachings of the present invention.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the presentinvention. As used herein, the singular forms “a,” “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises” and/or “comprising,” when used in this specification,specify the presence of stated features, integers, steps, operations,elements, and/or components, but do not preclude the presence oraddition of one or more other features, integers, steps, operations,elements, components, and/or groups thereof.

Example embodiments of the present invention are described herein withreference to cross-sectional illustrations that are schematicillustrations of idealized embodiments (and intermediate structures) ofthe present invention. As such, variations from the shapes of theillustrations as a result, for example, of manufacturing techniquesand/or tolerances, are to be expected. Thus, example embodiments of thepresent invention should not be construed as limited to the particularshapes of regions illustrated herein but are to include deviations inshapes that result, for example, from manufacturing. For example, animplanted region illustrated as a rectangle will, typically, haverounded or curved features and/or a gradient of implant concentration atits edges rather than a binary change from implanted to non-implantedregion. Likewise, a buried region formed by implantation may result insome implantation in the region between the buried region and thesurface through which the implantation takes place. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the actual shape of a region of a device andare not intended to limit the scope of the present invention.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

Chalcogenide Compound Target

A chalcogenide compound target according to example embodiments of thepresent invention may include carbon with a relative high content andmetal with a relatively low content.

According to some example embodiments, the chalcogenide compound targetmay include a chalcogenide compound in accordance with the followingchemical formula (1):

C_(A)M_(B)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (1)

In the above chemical formula (1), C indicates carbon and M representsmetal. Additionally, 8.0≦A≦40.0 and 0.1≦B≦20.0. Furthermore, 0.1≦X≦30.0and 0.1≦Y≦90.0. Example of the metal in the chalcogenide compound mayinclude aluminum (Al), gallium (Ga), indium (In), titanium (Ti), chrome(Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zirconium(Zr), molybdenum (Mo), ruthenium (Ru), palladium (Pd), hafnium (Hf),tantalum (Ta), iridium (Ir), platinum (Pt), etc. These may be used aloneor in a mixture thereof.

In an example embodiment, the chalcogenide compound target may include achalcogenide compound in which germanium in the chemical formula (1) issubstituted with germanium and silicon (Si) or germanium and tin (Sn).For example, the chalcogenide compound target may include a chalcogenidecompound according to the following chemical formula (2):

C_(A)M_(B)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (2)

In the above chemical formula (2), Z includes silicon or tin. Further,0.1≦X≦80.0 and 0.1≦Y≦90.0.

In an example embodiment, the chalcogenide compound target may include achalcogenide compound in which antimony in the chemical formula (1) issubstituted with antimony and arsenic (As) or antimony and bismuth (Bi).For example, the chalcogenide compound target may include a chalcogenidecompound according to the following chemical formula (3):

C_(A)M_(B)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B))   (3)

In the above chemical formula (3), T includes arsenic or bismuth.Additionally, 0.1≦X≦90.0 and 0.1≦Y≦80.0.

In an example embodiment, the chalcogenide compound target may include achalcogenide compound in which tellurium in the chemical formula (1) issubstituted with antimony and selenium (Se). For example, thechalcogenide compound target may include a chalcogenide compoundaccording to the following chemical formula (4):

C_(A)M_(B)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   (4)

In the above chemical formula (4), Q includes antimony and selenium(Se). Additionally, 0.1≦X≦30.0 and 0.1≦Y≦90.0.

According to other example embodiments of the present invention, thechalcogenide compound target may include carbon with a relativelycontent, metal with a relatively low content, and nitrogen with arelatively low content. For example, the chalcogenide compound targetmay include a chalcogenide compound in accordance with the followingchemical formula (5):

C_(A)M_(B)M_(C)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))   (5)

In the above chemical formula (5), C means carbon, M denotes metal and Nindicates nitrogen. Additionally, 8.0≦A≦30.0, 0.1≦B≦15.0 and 0.1≦C≦10.0.Furthermore, 0.1≦X≦30.0 and 0.1≦Y≦90.0.

In an example embodiment, the chalcogenide compound target may include achalcogenide compound in which germanium in the chemical formula (5) issubstituted with germanium and silicon (Si) or germanium and tin (Sn).For example, the chalcogenide compound target may include a chalcogenidecompound according to the following chemical formula (6):

C_(A)M_(B)N_(C)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))  (6)

In the above chemical formula (6), Z includes silicon or tin. Further,0.1≦X≦80.0 and 0.1≦Y≦90.0.

In an example embodiment, the chalcogenide compound target may include achalcogenide compound in which antimony in the chemical formula (5) issubstituted with antimony and arsenic (As) or antimony and bismuth (Bi).For example, the chalcogenide compound target may include a chalcogenidecompound according to the following chemical formula (7):

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)T_((100-y))Te_((100-X-Y))]_((100-A-B-C))  (7)

In the above chemical formula (7), T includes arsenic or bismuth.Additionally, 0.1≦X≦90.0 and 0.1≦Y≦80.0.

In an example embodiment, the chalcogenide compound target may include achalcogenide compound in which tellurium in the chemical formula (5) issubstituted with antimony and selenium (Se). For example, thechalcogenide compound target may include a chalcogenide compoundaccording to the following chemical formula (8):

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   (8)

In the chemical formula (8), Q includes antimony and selenium (Se).Additionally, 0.1≦X≦30.0 and 0.1≦Y≦90.0.

In some example embodiments of the present invention, the chalcogenidecompound target may include more than two of the chalcogenide compoundsaccording to the chemical formulae (1) to (8).

Method of Forming a Chalcogenide Compound Target

FIG. 1 is a flow chart illustrating a method of forming a chalcogenidecompound target in accordance with example embodiments of the presentinvention.

Referring to FIG. 1, a first compound powder, a second compound powderand a third compound powder are prepared in step S10. The first compoundpowder may include germanium carbide, and the second compound powder mayinclude antimony. Additionally, the third compound powder may includetellurium.

In some example embodiments of the present invention, the first compoundpowder may have a composition according to the following chemicalformula (9):

C_(A)Ge_((100-A))   (9)

In the above chemical formula (9),

In some example embodiments, a solution is prepared to form the firstcompound powder. The solution may include germanium alkoxide and carbonalkoxide. The solution may be dried at a temperature of about 50° C. toabout 500° C. for about 1 hour to about 6 hours so that the firstcompound power is obtained. Here, a screening process may beadditionally performed to advantageously adjust a particles size of thefirst compound powder. For example, the compound powder may have adesired particle size by a sieving process or a milling process.Further, the solution may be dried under a vacuum atmosphere or areduction atmosphere.

In some example embodiments, the first compound powder may be obtainedby calcinating a powder mixture after forming the powder mixture bymixing a germanium powder with a carbon powder such as a graphite powderwhile adding a solvent to the germanium powder and the carbon powder.For example, the powder mixture may be calcinated at a temperature ofabout 150° C. to about 2,000° C. under an inactive gas atmosphere or areduction atmosphere. Further, the powder mixture may be grinded using aball mill before calcinating the powder mixture.

In some example embodiments, the first compound powder may be preparedby calcinating a powder mixture after forming the powder mixture bydrying a solution in which a germanium powder and a metal carbide powderare dissolved therein. Examples of the metal carbide may includealuminum carbide, gallium carbide, indium carbide, titanium carbide,chrome carbide, manganese carbide, iron carbide, cobalt carbide, nickelcarbide, zirconium carbide, molybdenum carbide, ruthenium carbide,palladium carbide, hafnium carbide, tantalum carbide, iridium carbide,platinum carbide, etc. These may be used alone or in a mixture thereof.

In some example embodiments, the first compound powder may be obtainedby mixing nano-carbon powder and germanium powder, or by apolymerization process.

Referring now to FIG. 1, the first compound powder, the second compoundpowder and the third compound powder are mixed by adding a solvent,thereby obtaining a powder mixture in step S20. For example, the solventmay include deionized water, alcohol, acetone, etc. In an exampleembodiment, the first compound powder, the second compound powder andthe third compound powder may be mixed while grinding the first compoundpowder, the second compound powder and the third compound powder.

The powder mixture is inserted into a dryer in step S30, and then thedried powder mixture is molded to form a shaped body having a desiredstructure in step S40. For example, the powder mixture may be dried at atemperature of about 50° C. to about 500° C. for about 1 hour to about 6hours. In the drying process, the solvent is removed from the powdermixture. In an example embodiment, the powder mixture may not be moldedwhen the powder mixture is directly sintered.

In step S50, the shaped body or the powder mixture is sintered to form achalcogenide compound target. The chalcogenide compound target mayinclude a chalcogenide compound containing carbon. The chalcogenidecompound target may be formed by a sintering process performed at atemperature of about 150° C. to about 2,000° C. under an inactive gasatmosphere or a reduction atmosphere. For example, the sintering processmay include a furnace sintering process, a hot pressing process, a hotisostatic process, a reactive hot pressing process, etc.

In some example embodiments, the chalcogenide compound target may beobtained using a first compound powder having a composition in whichgermanium in the above chemical formula (9) is substituted withgermanium and silicon or germanium and tin. For example, thechalcogenide compound target may be obtained using a first compoundpowder having a composition according to the following chemical formula(10):

C_(A)[Ge_(X)Z_((100-X))]_((100-A))   (10)

In the above chemical formula (10), Z includes silicon or tin, and0.1≦X≦80.0.

In some example embodiments, the chalcogenide compound target may beformed using a chalcogenide compound obtained from a first powderincluding germanium, a second compound powder including antimonycarbide, and a third powder including tellurium. The second compoundpowder may have a composition in accordance with the following chemicalformula (11):

C_(A)Sb_((100-A))   (11)

In the above chemical formula (11), 8.0≦A≦50.0.

In some example embodiments, the chalcogenide compound target may beobtained using a second compound powder having a composition in whichantimony in the above chemical formula (11) is substituted with antimonyand arsenic, or antimony and bismuth. For example, the chalcogenidecompound target may be obtained using a second compound powder having acomposition according to the following chemical formula (12):

C_(A)[Sb_(Y)T_((100-X))]_((100-A))   (12)

In the above chemical formula (12), T includes arsenic or bismuth, and0.1≦Y≦80.0.

In some example embodiments, the chalcogenide compound target may beformed using a chalcogenide compound obtained from a first powderincluding germanium, a second powder including antimony, and a thirdcompound powder including tellurium carbide. The third compound powdermay have a composition in accordance with the following chemical formula(13):

C_(A)Te_((100-A))   (13)

In the above chemical formula (13), 8.0≦A≦50.0.

In some example embodiments, the chalcogenide compound target may beobtained using a third compound powder having a composition in whichtellurium in the above chemical formula (13) is substituted withantimony and selenium. For example, the chalcogenide compound target maybe obtained using a second compound powder having a compositionaccording to the following chemical formula (14):

C_(A)Q_((100-A))   (14)

In the above chemical formula (14), Q includes antimony and selenium,and 8.0≦A≦50.0.

In some example embodiments, the chalcogenide compound target may beformed using a chalcogenide compound obtained from a first powderincluding germanium, a second powder including antimony, a third powderincluding tellurium, and a fourth powder including metal carbide. Thefourth powder may have a composition in accordance with the followingchemical formula (15):

C_(A)M_((100-A))   (15)

In the above chemical formula (15), M indicates metal and 50.0≦A≦100.0.Examples of metal in the fourth powder may include aluminum, gallium,indium, titanium, chrome, manganese, iron, nickel, cobalt, zirconium,molybdenum, ruthenium, palladium, hafnium, tantalum, iridium, platinum,etc. These may be used alone or in a mixture thereof.

In some example embodiments, the chalcogenide compound target may beformed using a chalcogenide compound including carbon and metal, whichis obtained using a powder including antimony, a powder includingtellurium, a powder including germanium-silicon, and a metal carbidepowder having a composition in the above chemical formula (15).

In some example embodiments, the chalcogenide compound target may beformed using a chalcogenide compound including carbon and metal, whichis obtained using a powder including germanium, a powder includingtellurium, a powder including antimony-arsenic or antimony-bismuth, anda metal carbide powder having a composition in the above chemicalformula (15).

In some example embodiments, the chalcogenide compound target may beformed using a chalcogenide compound including carbon and metal, whichis obtained using a powder including germanium, a powder includingantimony, a powder including antimony and selenium, and a metal carbidepowder having a composition in the above chemical formula (15).

Method of Manufacturing a Phase-Change Memory Device

FIGS. 2A to 2K are cross-sectional views illustrating a method ofmanufacturing a phase-change memory device in accordance with exampleembodiments of the present invention.

Referring to FIG. 2A, an isolation layer 103 is formed on a substrate100 to define an active region and a field region. For example, thefield region may correspond to one portion of the substrate 100 on whichthe isolation layer 103 is positioned, whereas the active region maycorrespond to another portion of the substrate 100 enclosed by theisolation layer 103.

The substrate 100 may include a single crystalline metal oxide substrateor a semiconductor substrate such as a silicon substrate, a germaniumsubstrate, a silicon on insulator (SOI) substrate, a germanium oninsulator (GOI) substrate, etc.

The isolation layer 103 may be formed by an isolation process such as ashallow trench isolation (STI) process or a thermal oxidation process.The isolation layer 103 may be formed using an oxide such as siliconoxide.

A gate insulation layer (now illustrated), a gate conductive layer (notillustrated) and a gate mask layer (not illustrated) are successivelyformed on the substrate 100.

In one example embodiment, the gate mask layer, the gate conductivelayer and the gate insulation layer are patterned by a photolithographyprocess, thereby forming a gate insulation layer pattern 106, a gateelectrode 109 and a gate mask 112 on the active region of the substrate100. In another example embodiment, the gate mask layer may be etched toform the gate mask 112 on the gate conductive layer, and then the gateconductive layer and the gate insulation layer may be patterned usingthe gate mask 112 so as to form the gate insulation layer pattern 106and the gate electrode 109.

The gate insulation layer pattern 106 may include an oxide or a metaloxide. For example, the gate insulation layer pattern 106 may includesilicon oxide, aluminum oxide, zirconium oxide, hafnium oxide, tantalumoxide, etc.

The gate electrode 109 may include polysilicon doped with impurities, ametal or a metal compound. For example, the gate electrode 109 mayinclude tungsten, aluminum, copper, titanium, tantalum, tungstennitride, aluminum nitride, titanium nitride, tantalum nitride, titaniumaluminum nitride, etc. These may be used alone or in a mixture thereof.

The gate mask 112 r may include a material having an etching selectivityrelative to the gate insulation layer pattern 106 and the gate electrode109. For example, the gate mask 112 may include silicon nitride orsilicon oxynitride.

After a lower insulation layer (not illustrated) is formed on thesubstrate 100 to cover the gate mask pattern 112, lower insulation layeris etched to form a gate spacer 115 on sidewalls of the gate insulationlayer pattern 106, the gate electrode 109 and the gate mask 112. Forexample, the gate spacer 115 may be formed using a nitride such assilicon nitride. As a result, a gate structure 118 including the gateinsulation layer pattern 106, the gate electrode 109, the gate mask 112and the gate spacer 115 is provided on the active region of thesubstrate 100.

Impurities are implanted into portions of the substrate 100 adjacent tothe gate structure 118 such that a first contact region 121 and a secondcontact region 124 are formed at the portions of the substrate 100. Thefirst and the second contact regions 121 and 124 may be formed by an ionimplantation process. A lower electrode 160 (see FIG. 2D) may beelectrically connected to the first contact region 121, and a lowerwiring 142 (see FIG. 2B) may be electrically connected to the secondcontact region 124.

A lower insulating interlayer 130 is formed on the substrate 100 tocover the gate structure 118. The lower insulating interlayer 130 may beformed by a chemical vapor deposition (CVD) process, a plasma enhancedchemical vapor deposition (PECVD) process, a low pressure chemical vapordeposition (LPCVD) process, a high density plasma-chemical vapordeposition (HDP-CVD) process, etc. Further, the lower insulatinginterlayer 130 may be formed using an oxide such as silicon oxide. Forexample, the lower insulating interlayer 130 may be formed usingphosphor silicate glass (PSG), boro-phosphor silicate glass (BPSG),undoped silicate glass (USG), spin on glass (SOG), tetraethylorthosilicate (TEOS), plasma enhanced tetraethylortho silicate (PE-TEOS),flowable oxide (FOX), HDP-CVD oxide, etc. In an example embodiment, thelower insulating interlayer 130 may be planarized by a planarizationprocess. For example, the lower insulating interlayer 130 may have alevel surface by a chemical mechanical polishing (CMP) process and/or anetch-back process.

The lower insulating interlayer 130 is partially etched by aphotolithography process so that a first contact hole (not illustrated)and a second contact hole (not illustrated) are formed through the lowerinsulating interlayer 130. The first and the second contact holes exposethe first and the second contact regions 121 and 124, respectively.

A first lower conductive layer (not illustrated) is formed on the lowerinsulating interlayer 130 to fill up the first and the second contactholes. The first lower conductive layer may be formed using a metal, ametal compound or doped polysilicon. For example, the first lowerelectrode layer may be formed using tungsten, aluminum, copper,titanium, tantalum, tungsten nitride, aluminum nitride, titaniumnitride, tantalum nitride, titanium aluminum nitride, etc. These may beused alone or in a mixture thereof. The first lower electrode layer maybe formed by a sputtering process, a CVD process, an LPCVD process, anatomic layer deposition (ALD) process, an electron beam evaporationprocess, a pulsed-laser deposition (PLD) process, etc.

The first lower conductive layer is partially removed until the lowerinsulating interlayer 130 is exposed. Accordingly, a first pad 133 and asecond pad 136 are formed through the lower insulating interlayer 130.The first pad 133 filling the first contact hole is formed on the firstcontact region 121, and the second pad 136 filling the second contacthole is positioned on the second contact region 124.

Referring to FIG. 2B, a second lower conductive layer (not illustrated)is formed on the lower insulating interlayer 130, the first pad 133 andthe second pad 136. The second lower conductive layer may be formedusing a metal, a metal compound or doped polysilicon. For example, thesecond lower electrode layer may be formed using tungsten, aluminum,copper, titanium, tantalum, tungsten nitride, aluminum nitride, titaniumnitride, tantalum nitride, titanium aluminum nitride, etc. These may beused alone or in a mixture thereof. Further, the second lower electrodelayer may be formed by a sputtering process, a CVD process, an LPCVDprocess, an ALD process, an electron beam evaporation process, a PLDprocess, etc.

The second lower conductive layer is patterned by a photolithographyprocess to form a third pad 139 and the lower wiring 142. Since thirdpad 139 is formed on the first pad 133, the third pad 139 may beelectrically connected to the first contact region 121 through the firstpad 133. The lower wiring 142 locates on the second pad 136 so that thelower wiring 142 may make electrically contact with the second contactregion 133. In some example embodiments, the lower wiring 142 mayinclude a bit line. The third pad 139 and the lower wiring 142 may havewidths substantially wider than those of the first and the second pads133 and 136, respectively.

A first insulation layer 145 is formed on the lower insulatinginterlayer 130 to cover the third pad 139 and the lower wiring 142. Thefirst insulation layer 145 may be formed using an oxide. For example,the first insulation layer 145 may be formed using silicon oxide such asPSG, BPSG, USG, SOG, TEOS, PE-TEOS, FOX, HDP-CVD oxide, etc. Further,the first insulation layer 145 may be formed by a CVD process, a PECVDprocess, an LPCVD process, an HDP-CVD process, etc. In an exampleembodiment, an upper portion of the first insulation layer 145 may beplanarized by a CMP process and/or an etch-back process.

In some example embodiments of the present invention, the firstinsulation layer 145 may be formed using an oxide substantially the sameas that of the lower insulating interlayer 130. Alternatively, the firstinsulation layer 145 and the lower insulating interlayer 130 may beformed using different oxides, respectively.

A second insulation layer 148 and a sacrificial layer 151 aresequentially formed on the first insulation layer 145. The sacrificiallayer 151 may be formed using an oxide substantially the same as orsubstantially similar to that of the first insulation layer 145. Thesecond insulation layer 148 may be formed using a material having anetching selectivity relative to the first insulation layer 145 and thesacrificial layer 151. For example, the sacrificial layer 151 may beformed using PSG, BPSG, USG, SOG, TEOS, PE-TEOS, FOX, HDP-CVD oxide,etc. The second insulation layer 148 may be formed using a nitride suchas silicon nitride or silicon oxynitride. Further, the sacrificial layer151 may be formed by a CVD process, a PECVD process, an LPCVD process,an HDP-CVD process, etc. The second insulation layer 148 may be formedby a CVD process, a PECVD process, an LPCVD process, etc.

The first and the second insulation layers 145 and 148 may servetogether as a mold structure for forming the lower electrode 160.Additionally, the first and the second insulation layers 145 and 148 mayprotect underlying structures formed on the substrate 100 in successiveprocesses for forming the lower electrode 160. The sacrificial layer 151may also serve as the mold structure for forming the lower electrode160. The sacrificial layer 151 is removed from the second insulationlayer 148 after forming the lower electrode 160. In some exampleembodiments, each of the first insulation layer 145 and the sacrificiallayer 151 may be substantially thicker than the second insulation layer148.

After a photoresist pattern (not illustrated) is formed on thesacrificial layer 151, the sacrificial layer 151, the second insulationlayer 148 and the first insulation layer 145 are partially etched usingthe photoresist pattern as an etching mask. Hence, an opening (notillustrated) is formed through the first insulation layer 145, thesecond insulation layer 148 and the sacrificial layer 151. The openingexposes the third pad 139. After forming the opening, the photoresistpattern may be removed from the sacrificial layer 151 by an ashingprocess and/or a stripping process.

An upper insulation layer (not illustrated) is formed on the third pad139, a sidewall of the opening and the sacrificial layer 151, and thenthe upper insulation layer is partially etched to form a preliminaryspacer 154 on the sidewall of the opening. The upper insulation layermay be formed using a nitride such as silicon nitride. The preliminaryspacer 154 may be formed by an anisotropic etching process. Thepreliminary spacer 154 may reduce a width of the opening to therebyadjust a critical dimension of the lower electrode 160 formed in theopening When the preliminary spacer 154 is formed on the sidewall of theopening, the third pad 139 is exposed through the opening.

A lower electrode layer 157 is formed on the exposed third pad 139 andthe sacrificial layer 151 to fill up the opening. The lower electrodelayer 157 may be formed using a metal and/or a metal compound. Forexample, the lower electrode layer 157 may be formed using iridium,ruthenium, platinum, palladium, tungsten, titanium, tantalum, aluminum,titanium nitride, tantalum nitride, molybdenum nitride, niobium nitride,titanium silicon nitride, titanium aluminum nitride, titanium boronnitride, zirconium silicon nitride, tungsten silicon nitride, tungstenboron nitride, zirconium aluminum nitride, molybdenum silicon nitride,molybdenum aluminum nitride, tantalum silicon nitride, tantalum aluminumnitride, etc. These may be used alone or in a mixture thereof.Additionally, the lower electrode layer 157 may be formed by asputtering process, a CVD process, a PECVD process, an electron beamevaporation process, an ALD process, a PLD process, etc.

Referring to FIG. 2D, the lower electrode layer 157 is partially removeduntil the sacrificial layer 151 is exposed. Thus, a preliminary lowerelectrode (not illustrated) is formed to fully fill up the opening. Thepreliminary spacer 154 is positioned between the sidewall of the openingand the preliminary lower electrode. The preliminary lower electrode maybe formed by a CMP process and/or an etch- back process.

After a formation of the preliminary lower electrode, the sacrificiallayer 151 is removed from the second insulation layer 148. Thesacrificial layer 151 may be removed by a wet etching process using anetching solution including fluoride. Alternatively, the sacrificiallayer 151 may be removed by a dry etching process using an etching gascontaining fluoride. In the etching process for removing the sacrificiallayer 151, the second insulation layer 148 may effectively protect theunderlying structures formed on the substrate 100. When the sacrificiallayer 151 is removed, the preliminary lower electrode and thepreliminary spacer 154 are upwardly protruded from the second insulationlayer 148. For example, upper portions of the preliminary lowerelectrode and the preliminary spacer 145 may be protruded as pillarshapes.

The protruded portions of the preliminary lower electrode and thepreliminary spacer 154 are removed to form the lower electrode 160 and aspacer 163 on the third pad 136. The spacer 163 and the lower electrode160 may be formed by a CMP process and/or an etch-back process. Thesecond insulation layer 148 may serve as an etching stop layer whileforming the lower electrode 160 and the spacer 163. The lower electrode160 may electrically make contact with the first contact region 121through the first pad 133 and the third pad 139. The spacer 163 mayadjust the width of the lower electrode 160. In an example embodiment,the processes for forming the spacer 163 may be omitted when the openinghas a desired width for the lower electrode 160.

A phase-change material layer 166 is formed on the lower electrode 160,the spacer 163 and the second insulation layer 148. The phase-changematerial layer 166 may be formed using a chalcogenide compound by a PVDprocess or a CVD process.

In some example embodiments, the phase-change material layer 166 may heformed by a sputtering process using one target. That is, thephase-change material layer 166 may be formed using a chalcogenidecompound target including a chalcogenide compound that contains carbonand metal, or carbon, nitrogen and metal. For example, the phase-changematerial layer 166 may be formed using a chalcogenide compound targetincluding at least one chalcogenide compound according to the abovechemical formulae (1) to (8). Alternatively, the phase-change materiallayer 166 may be formed on the lower electrode 160 and the secondinsulation layer 148 using a chalcogenide compound target under anitrogen atmosphere.

When the phase-change material layer 166 is formed using chalcogenidecompound target including at least one chalcogenide compound accordingto the above chemical formulae (1) to (4), the phase-change materiallayer 166 may include a chalcogenide compound according to the followingchemical formulae (16) to (19) as the composition of the chalcogenidecompound target.

C_(A)M_(B)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (16)

In the above chemical formula (16), C indicates carbon and M denotesmetal. Examples of metal in the phase-change material layer 166 mayinclude aluminum, gallium, indium, titanium, chrome, manganese, iron,cobalt, nickel, zirconium, molybdenum, ruthenium, palladium, hafnium,tantalum, iridium, platinum, etc. These may be used alone or in amixture thereof. Additionally, 0.2≦A≦30.0, 0.1≦B≦50.0, 0.1≦X≦30.0 and0.1≦Y≦90.0.

C_(A)M_(B)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (17)

In the above chemical formula (17), Z includes silicon or tin. Further,0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦80.0 and 0.1≦Y≦90.0.

C_(A)M_(B)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B))   (18)

In the above chemical formula (18), T includes arsenic or bismuth.Additionally, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦90.0, and 0.1≦Y≦80.0.

C_(A)M_(B)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   (19)

In the above chemical formula (19), Q includes antimony and selenium.Further, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦90.0 and 0.1≦Y≦90.0.

When the phase-change material layer 166 is formed using chalcogenidecompound target including at least one chalcogenide compound accordingto the above chemical formulae (5) to (8), the phase-change materiallayer 166 may include a chalcogenide compound according to the followingchemical formulae (20) to (23) as the composition of the chalcogenidecompound target.

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))   (20)

In the chemical formula (20), C means carbon, M indicates metal and Ndenotes nitrogen. Further, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦C≦10.0,0.1≦X≦30.0 and 0.1≦Y≦90.0.

C_(A)M_(B)N_(C)[Ge_(X)Z_((100-X))Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))  (21)

In the above chemical formula (21), Z includes silicon or tin,0.1≦X≦80.0 and 0.1≦Y≦90.0. Additionally, 0.2≦A≦30.0, 0.1≦B≦15.0 and0.1≦C≦10.0.

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)T_((100-Y))Te_((100-X-Y))]_((100-A-B-C))  (22)

In the above chemical formula (22), T includes arsenic or bismuth,0.1≦X≦90.0 and 0.1≦Y≦80.0. Further, 0.2≦A≦30.0, 0.1≦B≦15.0 and0.1≦C≦10.0.

C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Q_((100-X-Y))]_((100-A-B))   (23)

In the above chemical formula (23), Q includes antimony and selenium.Further, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦C≦10.0, 0.1≦X≦90.0 and 0.1≦Y≦90.0.

In some example embodiments of the present invention, the phase-changematerial layer 166 may be formed on the lower electrode 160 and thesecond insulation layer 148 by a co-sputtering process using more thantwo targets. For example, the phase-change material layer 166simultaneously using a first target including carbon or metal carbide,and a second target including a chalcogenide compound. Alternatively,the phase-change material layer 166 may be formed simultaneously using afirst target including carbon or metal carbide, a second targetincluding a chalcogenide compound under a nitrogen atmosphere.

In the sputtering process, a reaction chamber may have a pressure ofabout 0.1 mTorr to about 100 mTorr and a temperature of about 30° toabout 400° C. Additionally, substantially different powers may beapplied to the first and the second target, respectively in thesputtering process. For example, a first power of about 100 W to about200 W may be applied to the first target, and a second power of about 20W to about 500 W may be applied to the second target.

When the phase-change material layer 166 is formed using the firsttarget including carbon or metal carbide, and the second targetincluding a chalcogenide compound, the sputtering yield of carbon may beconsiderably different from the sputtering yield of the chalcogenidecompound in the sputtering process. For example, the sputtering yield ofthe chalcogenide compound may be larger than that of carbon by about 20times to about 40 times. Therefore, the first target may have highcarbon content to obtain the phase-change material layer 166 havingdesired carbon content. Alternatively, a chalcogenide compound targetmay have carbon content considerably higher than that of chalcogenidecompound when the chalcogenide compound target simultaneously includescarbon and chalcogenide compound.

In some example embodiments, the substrate 100 may be revolved whileperforming the sputtering process using the first and the second targetsin order to form the phase-change material layer 166 having uniformcomposition and thickness.

When the phase-change material layer 166 is formed by simultaneouslyusing more than two targets, the phase-change material layer 166 may notbe damaged by particles physically deposited thereon because the targetincluding the chalcogenide compound has clean surface and the targetincluding carbon also has pure surface. Although the sputtering yield ofcarbon is different from that of chalcogenide compound, the sputteringrates of carbon and chalcogenide compound may be controlled by applyingdifferent powers to the targets, respectively. As a result, thephase-change material layer 166 may have more uniform composition andthickness. Further, the phase-change material layer 166 may have variouscompositions because several targets having various compositions may beused to form the phase-change material layer 166.

In some example embodiments, the phase-change material layer 166 may beformed on the lower electrode 160 and the second insulation layer 148 bya sputtering process simultaneously using a first target includingcarbon or metal carbide, a second target including germanium-telluriumand a third target including antimony-tellurium. Alternatively, thephase-change material layer 166 may be formed simultaneously using afirst target including carbon, a second target including metal and athird target including a chalcogenide compound. Furthermore, thephase-change material layer 166 may be formed simultaneously using afirst target including carbon, a second target including metal and athird target including a chalcogenide compound under a nitrogenatmosphere.

According to some example embodiments of the present invention, thephase-change material layer 166 is formed using a chalcogenide compounddoped with carbon and metal, or carbon, nitrogen and metal. Thus, thephase-change material layer 166 may have improved crystallizedtemperature and resistance considerably larger than those of theconventional phase-change material layer including a GST compound, or aGST compound doped with nitrogen.

Referring now to FIG. 2D, a second upper electrode film 169 and a secondupper electrode film 172 are sequentially formed on the phase-changematerial layer 166 including the above-described composition. Thus, anupper electrode layer 175 including the first and the second upperelectrode films 169 and 172 is provided on the phase-change materiallayer 166.

The first upper electrode film 169 may be formed using a metal, and thesecond upper electrode film 172 may be formed using a metal compound.For example, the first upper electrode film 169 may be formed usingaluminum, gallium, indium, titanium, chrome, manganese, iron, cobalt,nickel, zirconium, molybdenum, ruthenium, palladium, hafnium, tantalum,iridium, platinum, etc. These may be used alone or in a mixture thereofFurther, the second upper electrode film 172 may be formed usingaluminum nitride, gallium nitride, indium nitride, titanium nitride,chrome nitride, manganese nitride, iron nitride, cobalt nitride, nickelnitride, zirconium nitride, molybdenum nitride, ruthenium nitride,palladium nitride, hafnium nitride, tantalum nitride, iridium nitride,platinum nitride, tungsten nitride, niobium nitride, titanium siliconnitride, titanium aluminum nitride, titanium boron nitride, zirconiumsilicon nitride, tungsten silicon nitride, tungsten boron nitride,zirconium aluminum nitride, molybdenum silicon nitride, molybdenumaluminum nitride, tantalum silicon nitride, tantalum aluminum nitride,etc. These may be used alone or in a mixture thereof. The first and thesecond upper electrode films 169 and 172 may be formed by a sputteringprocess, a CVD process, a PECVD process, an electron beam evaporationprocess, an ALD process, a PLD process, etc.

Referring to FIG. 2E, a photoresist pattern (not illustrated) is formedon the second upper electrode film 172, and then the second upperelectrode film 172, the first upper electrode film 169 and thephase-change material layer 166 are patterned, thereby forming aphase-change material layer pattern 178 and an upper electrode 187 onthe lower electrode 160 and the second insulation layer 148. The upperelectrode 187 includes a first upper electrode film pattern 181 and asecond upper electrode film pattern 184.

In some example embodiments, the phase-change material layer pattern 178and the upper electrode 187 may have widths substantially wider thanthat of the lower electrode 160.

An upper insulating interlayer 190 is formed on the second insulationlayer 148 to cover the upper electrode 187. The upper insulatinginterlayer 190 may be formed by a CVD process, a PECVD process, an LPCVDprocess, an HDP-CVD process, etc. Further, the upper insulatinginterlayer 190 may be formed using an oxide such as PSG, BPSG, USG, SOG,TEOS, PE-TEOS, FOX, HAD-CVD, etc.

In one example embodiment, the upper insulating layer 190 may be formedusing an oxide substantially the same as that of the lower insulatinginterlayer 130, the sacrificial layer 151 and/or the first insulatinglayer 145. In another example embodiment, the upper insulating layer190, the lower insulating interlayer 130, the sacrificial layer 151and/or the first insulating layer 145 may be formed using differenceoxides, respectively.

The upper insulating interlayer 190 is partially etched by aphotolithography process to form an upper contact hole (notillustrated). The upper contact hole exposes the second upper electrodefilm pattern 184 of the upper electrode 187.

An upper pad 193 and an upper wiring 196 are formed on the upperelectrode 187 and the upper insulating interlayer 190. The upper pad 193filling the upper contact hole is positioned on the exposed upperelectrode 187. The upper wiring 196 is formed on the upper pad 193 andthe upper insulating layer 190. The upper pad 193 and the upper wiring196 may be formed using doped polysilicon, a metal and/or a metalcompound. For example, the upper pad 193 and the upper wiring 196 may beformed using tungsten, titanium, tantalum, aluminum, tungsten nitride,aluminum nitride, titanium nitride, tantalum nitride, molybdenumnitride, niobium nitride, titanium aluminum nitride, etc. These may beused alone or in a mixture thereof. Further, the upper pad 193 and theupper wiring 196 may be formed by a sputtering process, a CVD process,an ALD process, an electron beam evaporation process, a PLD process,etc. In one example embodiment, the upper wiring 196 and the upper pad193 may be integrally formed each other. In another example embodiment,the upper pad 193 is formed on the upper electrode 187, and then theupper wiring 196 is formed on the upper pad 193 and the upper insulatinginterlayer 190.

FIGS. 3A to 3D are cross-sectional views illustrating a method ofmanufacturing a phase-change memory device in accordance with exampleembodiments of the present invention. In FIGS. 3A to 3D, processes forforming an isolation layer 203, a gate structure 218, a first contactregion 221, a second contact region 224, a lower insulating interlayer230 on a substrate 200 may be substantially the same as the processesdescribed with reference to FIG. 2A.

The gate structure 218 is positioned on an active region of thesubstrate 200. The gate structure 218 includes a gate insulation layerpattern 206, a gate electrode 209, a gate mask 212 and a gate spacer215.

Referring to FIG. 3A, a first photoresist pattern (not illustrated) isformed on the lower insulating interlayer 230, and then the lowerinsulating interlayer 230 is partially etched using the firstphotoresist pattern as an etching mask. Thus, a lower contact hole (notillustrated) is formed through the lower insulating interlayer 230. Thelower contact hole exposes the second contact region 224. Here, thefirst contact region 221 is not exposed.

A first lower conductive layer (not illustrated) is formed on the lowerinsulating interlayer 230 to fill up the lower contact hole. The firstlower conductive layer may be formed using metal, metal compound ordoped polysilicon.

The first lower conductive layer is partially removed until the lowerinsulating interlayer 230 is exposed so that a lower pad 233 filling thelower contact hole is formed on the second contact region 224. The lowerpad 233 may electrically connect a lower wiring 236 (see FIG. 3B) to thesecond contact region 224.

Referring to FIG. 3B, a second lower conductive layer (not illustrated)is formed on the lower pad 233 and the lower insulating interlayer 230.The second lower conductive layer 233 is patterned by a photolithographyprocess to form the lower wiring 236 on the lower pad 233. For example,the lower wiring 236 may include a bit line.

In an example embodiment, the lower pad 233 and the lower wiring 236 maybe integrally formed each other. For example, a lower conductive layer(not illustrated) may be formed on the lower insulating interlayer 230to fill up the lower contact hole, and then the lower conductive layermay be patterned to simultaneously form the lower wiring 236 and thelower pad 233.

An insulation structure 239 is formed on the lower insulating interlayer230 to cover the lower wiring 236. The insulation structure 239 mayinclude at least one oxide layer, at least one nitride layer and/or atleast one oxynitride layer. In one example embodiment, the insulationstructure 239 may include an oxide layer covering the lower wiring 236and the lower insulating interlayer 230. In another example embodiment,the insulation structure 239 may include an oxide layer and a nitridelayer sequentially formed on the lower wiring 236 and the lowerinsulating interlayer 230. In still another example embodiment, theinsulation structure 239 may include a first oxide layer, a nitridelayer and a second oxide layer successively formed on the lowerinsulating interlayer 230 to cover the lower wiring 236. In stillanother example embodiment, the insulation structure 239 may include afirst oxide layer, an oxynitride layer and a second oxide layer. Instill another example embodiment, the insulation structure 239 mayinclude a first oxide layer, a second oxide layer, a first nitridelayer, a second nitride layer, a first oxynitride layer and/or a secondoxynitride layer alternately or sequentially formed on the lowerinsulating interlayer 230 to cover the lower wiring. Here, the first andthe second oxide layers may be formed using silicon oxide, and the firstand the second nitride layers may be formed using silicon nitride.Additionally, the first and the second oxynitride layers may be formedusing silicon oxynitride or titanium oxynitride.

After a second photoresist pattern (not illustrated) is formed on theinsulation structure 239, the insulation structure 239 and the lowerinsulating interlayer 230 are partially etched to form an opening (notillustrated) exposing the first contact region 221. The opening may beformed an anisotropic etching process.

A diode 242 is formed on the first contact region 221 to fill up theopening. The diode 242 may include polysilicon formed by a selectiveepitaxial growth (SEG) process. The first contact region 221 may serveas a seed for forming the diode 242. The diode 242 may have a heightsubstantially the same as a depth of the opening. Thus, upper faces ofthe diode 242 and the insulation structure 239 may be on a same plane.That is, the diode 242 may have a thickness substantially the same as atotal thickness of the lower insulating interlayer 230 and theinsulation structure 239.

Referring to FIG. 3C, a phase-change material layer (not illustrated) isformed on the diode 242 and the insulation structure 239 by a sputteringprocess. The phase- change material layer may be formed by a processsubstantially the same as the process described with reference to FIG.2C. Thus, the phase-change material layer may include at least onechalcogenide compound according to the above chemical formulae (19) to(23). For example, the phase-change material layer may include achalcogenide compound containing carbon and metal, or a chalcogenidecompound containing carbon, nitrogen and metal.

An upper electrode layer (not illustrated) including a first upperelectrode film and a second upper electrode film is formed on theinsulation structure 239 and the phase-change material layer. The upperelectrode layer may be formed by a process substantially the same as theprocess described with reference to FIG. 2D. Additionally, the first andthe second upper electrode films may be formed using materialssubstantially the same as those described with reference to FIG. 2D.

After a third photoresist pattern (not illustrated) is formed on theupper electrode layer, the second upper electrode film, the first upperelectrode film and the phase-change material layer are patterned usingthe third photoresist pattern as an etching mask. Thus, a phase-changematerial layer pattern 248 and an upper electrode 254 are formed on thediode 242 and a portion of the insulation structure 239 around the diode242. The upper electrode 254 includes a first upper electrode filmpattern 248 and a second upper electrode film pattern 251 sequentiallyformed on the phase-change material layer pattern 248.

Referring to FIG. 3D, an upper insulating interlayer 257 is formed onthe insulation structure 239 to cover the upper electrode 254. The upperinsulating interlayer 257 may be formed using an oxide by a CVD process,a PECVD process, an LPCVD process, an IIDP-CVD process, etc.

After a fourth photoresist pattern (not illustrated) is formed on theupper insulating interlayer 257, the upper insulating interlayer 257 ispartially etched using the fourth photoresist pattern as an etchingmask. Hence, an upper contact hole (not illustrated) is formed throughthe upper insulating interlayer 257 to expose the upper electrode 254.

An upper pad 260 filling the upper contact hole is formed on the upperelectrode 254, and an upper wiring 263 is formed on the upper pad 260and the upper insulating interlayer 257. The upper pad 260 and the upperwiring 263 may be integrally formed each other. For example, upper pad260 and the upper wiring 263 may be formed using doped polysilicon,metal and/or metal compound by a sputtering process, an LPCVD process, aCVD process, an ALD process, an electron beam evaporation process, a PLDprocess, etc. The upper wiring 263 may be electrically connected to theupper electrode 254 through the upper pad 260.

FIGS. 4A to 4C are cross-sectional views illustrating a method ofmanufacturing a phase-change memory device in accordance with exampleembodiments of the present invention. In FIGS. 4A to 4C, processes forforming an isolation layer 303, a gate structure 318, a first contactregion 321 and a second contact region 324, and a lower insulatinginterlayer 330 on a substrate 300 may be substantially the same as theprocesses described with reference to FIG. 2A. The gate structure 318 isformed on an active region of the substrate 300. The gate structure 318includes a gate insulation layer pattern 306, a gate electrode 309, agate mask 312 and a gate spacer 315.

Referring to FIG. 4A, the lower insulating interlayer 330 is partiallyetched to form a first contact hole and a second contact hole (notillustrated) through the lower insulating interlayer 330. The first andthe second contact holes expose the first and the second contact regions321 and 324, respectively.

A first lower conductive layer (not illustrated) is formed on the lowerinsulating interlayer 330 to fill up the first and the second contactholes. The first lower conductive layer may be formed using metal, metalcompound or doped polysilicon by a sputtering process, a CVD process, anLPCVD process, an ALD process, an electron beam evaporation process, aPLD process, etc.

The first lower conductive layer is partially removed until the lowerinsulating interlayer 330 is exposed so that a first pad 333 and asecond pad 336 arc formed through the lower insulating interlayer 330.The first pad 333 filling the first contact hole is formed on the firstcontact region 321, and the second pad 336 filling the second contacthole is positioned on the second contact region 324.

A second lower conductive layer (not illustrated) is formed on the lowerinsulating interlayer 330, the first pad 333 and the second pad 336. Thesecond lower conductive layer may be formed using metal, metal compoundor doped polysilicon by a sputtering process, a CVD process, an LPCVDprocess, an ALD process, an electron beam evaporation process, a PLDprocess, etc.

The second lower conductive layer is patterned to form a lower electrode339 and the lower wiring 342. The lower electrode 339 is formed on thefirst pad 333 such that the lower electrode 339 may be electricallyconnected to the first contact region 321 through the first pad 333. Thelower wiring 342 is positioned on the second pad 336 so that the lowerwiring 342 may make electrically contact with the second contact region333 through the second pad 336. The lower wiring 342 may include a bitline.

Referring to FIG. 4B, an insulation structure 345 is formed on the lowerinsulating interlayer 330 to cover the lower electrode 339 and the lowerwiring 242. The insulation structure 345 may include at least one oxidelayer, at least one nitride layer and/or at least one oxynitride layer.

After a photoresist pattern (not illustrated) is formed on theinsulation structure 345, the insulation structure 345 is partiallyetched using the photoresist pattern as an etching mask. Thus, anopening (not illustrated) exposing the lower electrode 339 is formedthrough the insulation structure 345. For example, the opening may beformed by an anisotropic etching process.

A phase-change material layer 166 is formed on the lower electrode 160,the spacer 163 and the second insulation layer 148. The phase-changematerial layer 166 may be formed using a chalcogenide compound by a PVDprocess or a CVD process.

A phase-change material layer 348 is formed on the lower electrode 339and the insulation structure 345 to fill up the opening The phase-changematerial layer 348 may be formed by a process substantially the same asthat described with reference to FIG. 2C. Further, the phase-changematerial layer 348 may have a composition substantially the same thephase-change material layer 157 illustrated in FIG. 2C.

Referring to FIG. 4C, the phase-change material layer 348 is partiallyremoved until the insulation structure 345 is exposed to form aphase-change material layer pattern 351 on the lower electrode 339. Forexample, the phase-change material layer pattern 351 may be formed by achemical mechanical polishing (CMP) process and/or an etch-back process.

A first upper electrode film (not illustrated) and a second upperelectrode film (not illustrated) are successively formed on thephase-change material layer pattern 351. The first and the second upperelectrode films are patterned to form an upper electrode 360 on theinsulation structure 345 and the phase-change material layer pattern351. The upper electrode includes a first upper electrode film pattern354 and a second upper electrode film pattern 357. In some exampleembodiments, each of the lower electrode 339 and the upper electrode306may have a width substantially wider than that of the phase-changematerial layer pattern 351.

An upper insulating interlayer 363 is formed on the insulation structure345 to cover the upper electrode 360. The upper insulating interlayer363 may be formed using oxide by a CVD process, a PECVD process, anLPCVD process, an HDP-CVD process, etc. In one example embodiment, theupper insulating layer 363 may be formed using an oxide substantiallythe same as that of the lower insulating interlayer 330. In anotherexample embodiment, the upper insulating layer 363 and the lowerinsulating interlayer 330 may be formed using difference oxides,respectively.

The upper insulating interlayer 363 is partially etched by aphotolithography process to form an upper contact hole (not illustrated)that exposes the upper electrode 360.

An upper pad 366 is formed on the upper electrode 360 to fill up theupper contact hole, and an upper wiring 369 is formed on the upper pad366 and the upper insulating layer 363. The upper wiring 369 and theupper pad 366 may be integrally formed each other.

According to the present invention, a chalcogenide compound target mayinclude a chalcogenide compound that contains carbon and metal, orcarbon, metal and nitrogen considering contents of carbon, metal andnitrogen. When a phase- change material layer is formed using thechalcogenide compound target by various sputtering processes, the phasetransition of the phase-change material layer may be stably repeated andalso the phase-change material layer may have enhanced crystallizedtemperature and resistance. Further, a phase-change memory device mayhave reduced set resistance and driving current while improvingdurability and sensing margin when the phase-change material layer isemployed in the phase- change memory device.

The foregoing is illustrative of the present invention and is not to beconstrued as limiting thereof. Although a few example embodiments of thepresent invention have been described, those skilled in the art willreadily appreciate that many modifications are possible in the exampleembodiments without materially departing from the novel teachings andadvantages of this invention. Accordingly, all such modifications areintended to be included within the scope of the present invention asdefined in the claims. In the claims, means-plus-function clauses areintended to cover the structures described herein as performing therecited function and not only structural equivalents but also equivalentstructures. Therefore, it is to be understood that the foregoing isillustrative of the present invention and is not to be construed aslimited to the specific embodiments disclosed, and that modifications tothe disclosed embodiments, as well as other embodiments, are intended tobe included within the scope of the appended claims. The presentinvention is defined by the following claims, with equivalents of theclaims to be included therein.

1. A method of manufacturing a phase-change memory device, comprising:forming a contact region on a substrate; forming a lower electrodeelectrically connected to the contact region; forming a phase-changematerial layer on the lower electrode using a chalcogenide compoundtarget including carbon and metal, or carbon, nitrogen and metal; andforming an upper electrode on the phase-change material layer.
 2. Themethod of claim 1, wherein the phase-change material layer comprises achalcogenide compound in accordance with the following chemical formula(16):C_(A)M_(B)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B))   (16) wherein Cindicates carbon, M represents metal, 0.2≦A≦30.0, 0.1≦B≦15.0, 0.1≦X≦30.0 and 0.1≦Y≦90.0.
 3. The method of claim 1, wherein thephase-change material layer comprises a chalcogenide compound inaccordance with the following chemical formula (17):C_(A)M_(B)N_(C)[Ge_(X)Sb_(Y)Te_((100-X-Y))]_((100-A-B-C))   (17) whereinC means carbon, M denotes metal, N indicates nitrogen 0.2≦A≦30.0,0.1≦B≦15.0, 0.1≦C≦10.0, 0.1≦X≦30.0 and 0.1≦Y≦90.0.
 4. A method ofmanufacturing a phase-change memory device, comprising: forming acontact region on a substrate; forming a lower electrode electricallyconnected to the contact region; forming a phase-change material layeron the lower electrode by a sputtering process using a first targetincluding carbon or metal carbide, and a second target including achalcogenide compound; and forming an upper electrode on thephase-change material layer.
 5. The method of claim 4, wherein a firstpower is applied to the first target, and a second power substantiallydifferent from the first power is applied to the second target.
 6. Themethod of claim 4, wherein the first power is in a range of about 100 Wto about 2,000 W and the second power is in a range of about 20 W toabout 500 W.
 7. The method of claim 4, wherein the metal carbidecomprises a composition in accordance with the following chemicalformula (18):C_(A)M_((100-A))   (18) wherein M indicates metal, and 50.0≦A≦100.0.